Lyotropic Boron Nitride Nanotube Liquid Crystals: Preparation, Characterization, and Wet-Spinning for Fabrication of Composite Fiber.

Microfiber fabrication via wet-spinning of lyotropic liquid crystals (LCs) with anisotropic nanomaterials has gained increased attention due to the microfibers' excellent physical/chemical properties originating from the unidirectional alignment of anisotropic nanomaterials along the fiber axis with high packing density. For wet-spinning of the microfibers, however, preparing lyotropic LCs by achieving high colloidal stability of anisotropic nanomaterials, even at high concentrations, has been a critically unmet prerequisite, especially for recently emerging nanomaterials. Here, we propose a cationically charged polymeric stabilizer that can efficiently be adsorbed on the surface of boron nitride nanotubes (BNNTs), which provide steric hindrance in combination with Coulombic repulsion leading to high colloidal stability of BNNTs up to 22 wt %. The BNNT LCs prepared from the dispersions with various stabilizers were systematically compared using optical and rheological analysis to optimize the phase behavior and rheological properties for wet-spinning of the BNNT LCs. Systematic optical and mechanical characterizations of the BNNT microfibers with aligned BNNTs along the fiber axis revealed that properties of the microfibers, such as their tensile strength, packing density, and degree of BNNT alignment, were highly dependent on the quality of BNNT LCs directly related to the types of stabilizers.

Composition of Organically Modified Silica for the Superhydrophobic Surface with Low Sliding Angle.

Extremely water-repellent surfaces with low sliding angle (SA) have been obtained with a facile single-step sol-gel strategy via co-condensation of tetraethoxysilane (TEOS) and hexadecyltrimethoxysilane (HDTMS) in basic media with an efficient self-cleaning property. We investigated the effect of the molar ratio of HDTMS and TEOS on the properties of the modified silica-coated poly(ethylene terephthalate) (PET) film. A high water contact angle (WCA) of 165° and a low SA of 1.35° were obtained at a molar ratio of 0.125. The dual roughness pattern for the low SA was developed by a one-step coating of the modified silica with a molar ratio of 0.125. The evolution of the surface to the dual roughness pattern by nonequilibrium dynamics depended on the size and shape factor of modified silica. The primitive size and the shape factor of the organosilica with a molar ratio of 0.125 were 70 nm and 0.65, respectively. We also presented a new method to determine the superficial surface friction (ζ) of the superhydrophobic surface. The ζ was a physical parameter that characterized the slip and rolling behavior of water droplets on the superhydrophobic surface along with the equilibrium property WCA and the static frictional property SA.

Ultrahigh strength, modulus, and conductivity of graphitic fibers by macromolecular coalescence.

Theoretical considerations suggest that the strength of carbon nanotube (CNT) fibers be exceptional; however, their mechanical performance values are much lower than the theoretical values. To achieve macroscopic fibers with ultrahigh performance, we developed a method to form multidimensional nanostructures by coalescence of individual nanotubes. The highly aligned wet-spun fibers of single- or double-walled nanotube bundles were graphitized to induce nanotube collapse and multi-inner walled structures. These advanced nanostructures formed a network of interconnected, close-packed graphitic domains. Their near-perfect alignment and high longitudinal crystallinity that increased the shear strength between CNTs while retaining notable flexibility. The resulting fibers have an exceptional combination of high tensile strength (6.57 GPa), modulus (629 GPa), thermal conductivity (482 W/m·K), and electrical conductivity (2.2 MS/m), thereby overcoming the limits associated with conventional synthetic fibers.

High-Resolution 3D Printing of Mechanically Tough Hydrogels Prepared by Thermo-Responsive Poloxamer Ink Platform.

High-resolution 3D-printable hydrogels with high mechanical strength and biocompatibility are in great demand because of their potential applications in numerous fields. In this study, a material system comprising Pluronic F-127 dimethacrylate (FDMA) is developed to function as a direct ink writing (DIW) hydrogel for 3D printing. FDMA is a triblock copolymer that transforms into micelles at elevated temperatures. The transformation increases the viscosity of FDMA and preserves its structure during DIW 3D printing, whereupon the printed structure is solidified through photopolymerization. Because of this viscosity shift, various functionalities can be incorporated through the addition of other materials in the solution state. Acrylic acid is incorporated into the pregel solution to enhance the mechanical strength, because the carboxylate group of poly(acrylic acid) ionically crosslinks with Fe3+ , increasing the toughness of the DIW hydrogel 37 times to 2.46 MJ m-3 . Tough conductive hydrogels are also 3D printed by homogenizing poly(3,4-ethylenedioxythiophene) polystyrene sulfonate into the pregel solution. Furthermore, the FDMA platform developed herein uses DIW, which facilitates multicartridges 3D printing, and because all the materials included are biocompatible, the platform may be used to fabricate complex structures for biological applications.

Tube-rolling and formation of mechanically robust micro-tubes in graphene oxide aqueous dispersions during shear flow.

We showed that GO domains at low pH are under a tube-rolling motion with a vorticity alignment at low shear rates. Mechanically robust micro-tubes were formed during tube-rolling. The micro-tubes were highly bendable and exhibited excellent elastic recovery. There was no restacking of GO sheets to graphitic structures for the GO micro-tube wall in a wet state.

Elastic particle deformation in rectangular channel flow as a measure of particle stiffness.

In this study, we experimentally observed and characterized soft elastic particle deformation in confined flow in a microchannel with a rectangular cross-section. Hydrogel microparticles of pNIPAM were produced using two different concentrations of crosslinker. This resulted in particles with two different shear moduli of 13.3 ± 5.5 Pa and 32.5 ± 15.7 Pa and compressive moduli of 66 ± 10 Pa and 79 ± 15 Pa, respectively, as measured by capillary micromechanics. Under flow, the particle shapes transitioned from circular to egg, triangular, arrowhead, and ultimately parachute shaped with increasing shear rate. The shape changes were reversible, and deformed particles relaxed back to circular/spherical in the absence of flow. The thresholds for each shape transition were quantified using a non-dimensional radius of curvature at the tip, particle deformation, circularity, and the depth of the concave dimple at the trailing edge. Several of the observed shapes were distinct from those previously reported in the literature for vesicles and capsules; the elastic particles had a narrower leading tip and a lower circularity. Due to variations in the shear moduli between particles within a batch of particles, each flow rate corresponded to a small but finite range of capillary number (Ca) and resulted in a series of shapes. By arranging the images on a plot of Ca versus circularity, a direct correlation was developed between shape and Ca and thus between particle deformation and shear modulus. As the shape was very sensitive to differences in shear modulus, particle deformation in confined flow may allow for better differentiation of microparticle shear modulus than other methods.

Generation and characterization of monodisperse deformable alginate and pNIPAM microparticles with a wide range of shear moduli.

Monodisperse particles of varying size, shape, and deformability were produced using two microfluidic strategies. For both strategies, monodisperse emulsion droplets of a crosslinkable solution were generated via flow-focusing. Subsequently, droplets were crosslinked either on chip or in an external bath. On-chip gelation resulted in spherical particles; varying the degree of crosslinking varied the deformability systematically. The optimized flow-focusing device design separated the production of monodisperse aqueous alginate droplets and the on-chip introduction of crosslinking ions. Two features were then adapted to target softer particles: the dispersed phase design and the polymer choice. The alternative design used a sheathed dispersed phase, with the polymer solution surrounding an unreactive viscous core, which generated alginate particles with a softer core. Poly(N-isopropylacrylamide) (pNIPAM) allowed access to a broad range of moduli. The resulting spherical particles were characterized using capillary micromechanics to determine the shear (G) and compressive (K) moduli. Particles with G = 0.013 kPa to 26 kPa and K = 0.221 kPa to 34.9 kPa were obtained; the softest particles are an order of magnitude softer than those previously reported. The second approach, based on earlier work by Hu et al., produced axisymmetric, non-spherical particles with fore-aft asymmetry. Alginate drops were again formed in a flow-focusing device but were crosslinked off-chip in an external gelation bath. By changing the bath viscosity, crosslinker concentration, and outlet height, the falling droplets deformed differently during gelation, resulting in a variety of shapes, such as teardrop, mushroom, and bowl shapes.

Tailored CVD graphene coating as a transparent and flexible gas barrier.

The chemical vapor deposition (CVD) method to obtain tailored graphene as a transparent and flexible gas barrier has been developed. By separating nucleation step from growth, we could reduce early graphene nucleation density and thus induce better stitching between domain boundaries in the second growth step. Furthermore, two step growth in conjunction with electrochemical polishing of Cu foils achieved large graphene domains and improved graphene quality with minimized defects. The performance of resulting graphene as a gas barrier was superior to the graphene obtained by one-step growth on polished or unpolished Cu foils. The CVD graphene reported here could open up the possibility for exploring graphene-based gas barrier due to the minimized density of defect area.

Highly bendable bilayer-type photo-actuators comprising of reduced graphene oxide dispersed in hydrogels.

To avoid the problem of reduced graphene oxide (rGO) restacking in aqueous solution, the preparation of light-responsive poly(N-isopropylacrylamide) incorporating rGO (PNIPAm/rGO) was achieved by the chemical reduction of GO dispersed in the hydrogel matrix. Due to the enhanced photothermal efficiency of the rGO, the prepared PNIPAm/rGO underwent large volume reductions in response to irradiation by visible light of modest intensity. With respect to potential applications, bilayer-type photo-actuators comprising a PNIPAm/rGO active layer and poly(acrylamide) passive layer were fabricated; these achieved a full bending motion upon visible-light exposure. Adjusting the swelling ratio of each layer in the initial state yielded bidirectional photo-actuators that showed the active motion of turning inside out. Furthermore, we demonstrated that the fabricated actuation system would exhibit controlled bending motion in response to solar radiation.

Fingertip skin-inspired microstructured ferroelectric skins discriminate static/dynamic pressure and temperature stimuli.

In human fingertips, the fingerprint patterns and interlocked epidermal-dermal microridges play a critical role in amplifying and transferring tactile signals to various mechanoreceptors, enabling spatiotemporal perception of various static and dynamic tactile signals. Inspired by the structure and functions of the human fingertip, we fabricated fingerprint-like patterns and interlocked microstructures in ferroelectric films, which can enhance the piezoelectric, pyroelectric, and piezoresistive sensing of static and dynamic mechanothermal signals. Our flexible and microstructured ferroelectric skins can detect and discriminate between multiple spatiotemporal tactile stimuli including static and dynamic pressure, vibration, and temperature with high sensitivities. As proof-of-concept demonstration, the sensors have been used for the simultaneous monitoring of pulse pressure and temperature of artery vessels, precise detection of acoustic sounds, and discrimination of various surface textures. Our microstructured ferroelectric skins may find applications in robotic skins, wearable sensors, and medical diagnostic devices.

Pulmonary Responses of Sprague-Dawley Rats in Single Inhalation Exposure to Graphene Oxide Nanomaterials.

Graphene is receiving increased attention due to its potential widespread applications in future. However, the health effects of graphene have not yet been well studied. Therefore, this study examined the pulmonary effects of graphene oxide using male Sprague-Dawley rats and a single 6-hour nose-only inhalation technique. Following the exposure, the rats were allowed to recover for 1 day, 7 days, or 14 days. A total of three groups were compared: control (fresh air), low concentration (0.46 ± 0.06 mg/m(3)), and high concentration (3.76 ± 0.24 mg/m(3)). The exposure to graphene oxide did not induce significant changes in the body weights, organ weights, and food consumption during the 14 days of recovery time. The microalbumin and lactate dehydrogenase levels in the bronchoalveolar lavage (BAL) fluid were not significantly changed due to the exposure. Similarly, total cell count, macrophages, polymorphonuclear leukocytes, and lymphocytes were not significantly altered in the BAL fluid. Plus, the histopathological examination of the rat lungs only showed an uptake of graphene oxide in the alveolar macrophages of the high-concentration group. Therefore, these results demonstrate that the single inhalation exposure to graphene oxide induce minimal toxic responses in rat lungs at the concentrations and time points used in the present study.

5-Day repeated inhalation and 28-day post-exposure study of graphene.

Graphene has recently been attracting increasing attention due to its unique electronic and chemical properties and many potential applications in such fields as semiconductors, energy storage, flexible electronics, biosensors and medical imaging. However, the toxicity of graphene in the case of human exposure has not yet been clarified. Thus, a 5-day repeated inhalation toxicity study of graphene was conducted using a nose-only inhalation system for male Sprague-Dawley rats. A total of three groups (20 rats per group) were compared: (1) control (ambient air), (2) low concentration (0.68 ± 0.14 mg/m(3) graphene) and (3) high concentration (3.86 ± 0.94 mg/m(3) graphene). The rats were exposed to graphene for 6 h/day for 5 days, followed by recovery for 1, 3, 7 or 28 days. The bioaccumulation and macrophage ingestion of the graphene were evaluated in the rat lungs. The exposure to graphene did not change the body weights or organ weights of the rats after the 5-day exposure and during the recovery period. No statistically significant difference was observed in the levels of lactate dehydrogenase, protein and albumin between the exposed and control groups. However, graphene ingestion by alveolar macrophages was observed in the exposed groups. Therefore, these results suggest that the 5-day repeated exposure to graphene only had a minimal toxic effect at the concentrations and time points used in this study.

Energy efficient glazing for adaptive solar control fabricated with photothermotropic hydrogels containing graphene oxide.

Glazing for adaptive solar control is the most promising for energy efficient development, because the use of this technology in buildings can be expected to significantly impact energy use and efficiency by screening sunlight that enters a building in summer. To achieve autonomous adjustable transparency, we have developed photothermotropic material system by combining photothermal materials with thermotropic hydrogels. We found that graphene oxide dispersed within a hydrogel matrix effectively converts the photo energy of sunlight into thermal energy, providing the efficient means to trigger transparency of thermotropic hydrogels. Therefore, we could develop switchable glazing of novel photothermotropic mechanism that screen strong sunlight and heat radiation in response to the sunlight intensity, as well as the temperature. Furthermore, in this study, a prototype device was manufactured with developed materials and successfully operated in outdoor testing.

Size of a crystal nucleus in the isothermal crystallization of supercooled liquid.

We present an alternative to classical nucleation theory (CNT). We introduce a size-dependent surface energy into the total Gibbs free-energy of formation of a crystal (ΔG). We consider the free-energy in the core part of the total volume of crystal and the free-energy in the surface-layer part of it, separately, for the evaluation of ΔG. As a result, we present an explicit model to evaluate a characteristic size of an initial nucleus that differs from the critical nucleus of CNT, but whose temperature dependence agrees well with that reported for the temperature dependency initial fold length of isotactic polystyrene and polyethylene in the literature. Our model has fitted the experimental data in the literature with only one adjustable parameter that is defined as nucleation constant. The nucleation constant is the Gibbs free-energy difference between the crystal and supercooled liquid phases for the volume of initial nucleus. We also present an expression to approximate the evolution of free-energy in the surface-layer part of crystal during the crystal growth.

Dispersion of multiwalled carbon nanotubes in aqueous silk fibroin solutions.

A simple method was developed to densely assemble multiwalled carbon nanotubes (MWCNTs) onto single native spider silk and silkworm silk fibers in aqueous system. The interactions between the MWCNTs and the silk fibroin were investigated using scanning electron microscopy and transmission electron microscopy. Furthermore, the role of pure silk fibroin in dispersing MWCNTs in aqueous systems was also assessed.